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3,100,’? 7 8
ite discs
Patented Aug. 13, 1963
2
1
values 0' (of the R1‘ substituents \atttached to q substituent
positions, the, ‘appropriate values for said Ri substituents
attached to said q positions being selected —?rorn said
Table I; ‘and 3.41 is a pnoportion'ality constant which up
plies when the thermal stability of the ‘Ri substituted
3,100,778
DERIVATWES @F 1,3,3 TRIMETHYDSPIRO
(2’H-1’-BENZUPYRAN-2,2’-INDULENE)
Elliot Berman, East Braintree, Mass, assignor to The
National Cash Register Company, Dayton, Ohio, a
compound is measured us an ethanol solution, has the
corporation of Maryland
No Drawing. Filed May 9, 1961, Ser. No. 108,710
desired characteristics, Whereas compounds that do not
satisfy the expression do not have the desired charac
6 Claims. (Cl. 260-319)
teristics.
H3O
,
The suhstituent constant sigma values a are derived
This invention relates to a compound of the structure 10
from the Hammett equation azlog Iii-dog K10, in which
CH3
Ki is the ionization constant for a substituted amniotic
reactant and K," is the ionization constant for an un
substituted aromatic reactant. More detailed information
15 about substituent constants and the derivation and inter
pretation thereof may be obtained by reference to Ham
CH3
mett, Physical Organic Chemistry, First Edition, pages
-
186 to 205, McGraw-Hill Book Company, Incorporuted,
New
York, N.Y., 1940; :and to Hine, Physical Organic
class so that the compound has a substantially colorless 20 Chemistry, First Edition, pages ‘69 to 80, 1956, also
state, in which the 2'-l’ bond is intact, and a distinctively
published by McGnaw-Hill Book Company.
colored state, in which the 2'-1’ bond is broken, the
colored state being produced, at
by irnadieting a
TABLE I
v
solution of the compound with electromagnetic radiation
Substituent
Constant
Sigma
Values=u
having a preponderance of blue and ultna~violet compo 25
nents, land the colorless state being redeveloped, lat Will,
in which the Rt‘ snbstituents are selected from a de?ned
by irradiating a solution of the compound with electro
magnetic radiation having a preponderance of wave
Rin g D ositions
M
8’
lengths longer than blue.
This is a continuation-impart of United States patent 30
application Serial No. 803,836, filed by Elliot Ber-man on
April 3, 1959, now ‘abandoned.
The claimed composition is unique not only in that
(1) CH3 ___________________ __
5’; 7'
—0. 17
6’
—O. 009
—0. 306
—0, 0025
—0; 291
(3) CH(CHa)i__
—O. 0589
—0. 276
(4) C(OHQa (5) O H
—0. 0581
+006
~0. 250
—0. 01
+0.43
+0.56
+0. 376
+0.54
+0.66
+0. 502
+0.37
+0.45
—O. 16
—0. 66
‘
.
(6) OF
the change in state may be brought about, repeatedly, in
ON
the temperature range of from plus 20 ‘degrees centignade 35 (7)
(8) OOCHq
(9) 00202115.
to minus 20 degrees centignade and below, by the speci?ed
(10) 00
electromagnetic radiation, but in that in many instances
(11) NH; ___________________ __
(12) NHCH5__
the composition is stable ‘at least for several months, in
(13) N(CH3)»
solution, against change from one state to the other state
(14) NHOOOH3 ________________________ -_
(15) NO: ____________________ __
+0. 80
by thermal activity thereof in that temperature range, in 40 (16)
OOH3_-__
—0.39
the absence of counteracting electromagnetic radiation.
.
.
By “solution,” as used herein, is meant the homogeneous
+0. 37
+0.45
—0. 84
—0.83
+0.21
0.0
+0. 662
+0. 777
+0. 0465
—0.764
+0.1
—024
mixture of one or more of the compounds with a solid or
+01
+0. 252
+0. 121
—0. 25
—O. 32
—0, 37
liquid substance. The claimed compound, with the speci
+0. 39
+0.31
?ed characteristics, behaves according to the energy con
tribution which the substituents Ri ‘give to the parent
compound, and such enemgy contributions can be cal
culated from known values in the position or positions
which they occupy in the structure of the parent com
pound relative to the site of reaction, which site is at
the mentioned 2’-1' bond.
+0.15
0.0
+0.25
+0.39
+0.
+0.44
+0.52
‘ccording to the invention, a compound Within the
(35) OOZOHQ _______________ ._
7
D1I/
/ \1
0
8, 7,6
H3O
I,
l
CH3
and, when dissolved in ethanol, satisfying the expression
3109923341 E ¢r( Rt‘, q) 35.19343
+0.57
+0391
+0. 352
+0.70
+0148
+0. 132
+0.76
-0. 0714
+0. 112
—O. 0625
—0. 291
+0.37
+0.45
A preferred class of such compounds includes photo
tropic compounds having the genenal structural formula:
3
Ri
s
+0.49
+0.72
+0. 337
+0. 373
‘structure
4
+0, 52
+0. 60
+0.40
CH3
\/
60
‘
v
4 /a\
5
r
\
6
.1771’
2G2\1'
\7/\§/
°
.
R1
s
8’ 7'6"
éHa
5’Sq£8’
65 wherein R, represents independently-selected substituent
‘ radicals in at least two of substituent positions 5', 6', 7’,
where Ri represents ‘one or more of the substituent radicals
R listed in Table I, which follows; q represents the sub
end 8', said substituent radicals being selected from the
stituent positions 5', 6’, 7’, and 8’;
group consisting of —NO2, —OCH3, —Cl, —Br, -I,
and —F, the substituents at said positions consisting of
$51138’
represents the sum of the substituent constant sigma
70 (a) at least one but no more than two --NO2 groups
and (Z2) at least one of the foregoing radicals: other than
the ——NO2 radical, the substituent radicals being so
3,100,778
.
.
,
u
'
selected that the compound, when dissolved in ethanol,
satis?es the expression:
4)
'
(
NO 2—
OH O
3109925341s'sqss'
E 0(121", @5519343
——OH
|
where Ri represents the substituent radicals, q stands for
the substituent positions, and
Br
3—brom0-5-nitrosa1icylaldehyde
(5)
N02
2 a( R2‘, q)
'
b'sqss'
01
represents the sum of the substituent constant sigma
values of said Ri ‘substituent radicals when attached to
any one of positions 5', 6', 7', land 8’, the sigma values
of said substituents when attached at the different positions
15
being as follows:
Ri
, 8’
'5' z 7'
+0. 80 -
+0. 20
+0. 21
+0. 21
+0. 24
—OH
I
01
3,5~dich1or0-G-nltrosalicylaldehyde
As an example of one of the claimed compounds within
the
‘of the expression, and which has an expression
value of 5.19343 according to the sigma values in Table
6’
+0. 662
, —0. 39
—CHO
+0. 777
+0. 0465
-0. 764
+0. 373
+0. 391
+0. 352
+0. 337
+0. 112
+0148
+0. 132
—0, 0714
I, is the 5',7’-dichloro, 6’-nitro derivative which has the
20 structure
CH3
Any substituted spiro-pyran compound falling within
the scope of the inst-ant disclosure is suitable for the stated
purposes. However, those compounds which are particu
larly suitable and which are thus especially preferred may
be selected from the group consisting of
_( 1)
1,3,3-t1imethyl-indoline - 5',7'-dichloro46'-nitrobenzo
and which expression value of 5.19343 is at the high limit,
This com
pound in ?nely divided form is a substantially colorless
material,‘ solid in the temperature ranges speci?ed, and
30 ‘of those compounds within the expression.
ryryllospiran;
(2) 1,3,3-trimethylindolinoe8'-methoxy-5’,6'-dinitrobenzo
-
forms a colorless solution in toluene which turns to a
pyrylespiran;
(3) 1,3,3~tnimethvlindolino-8'-fluoro~6’-nitrobenzopyrylo
(4) l,3,3-trimethylindolino-8'-brorno-6'-nitrobenzopyrylo
sriran;
.
dark blue when irradiated with light having \a preponder
35 ance of ultraviolet components, and is reversible in such
,
spiran;
solution to the colorless state by subsequent irradiation
with light having predominately visible or infra-red com
ponents.
This 5',7’-diohloro, 6’-nitro derivative is stable in either
_
(5) 1,3,3 - trimethylindolino - 6',8'-chloro - 5'-nitrobenzo
pyrylospiran.
40 the colorless‘ or the colored form, at room temperature
In preparing theiabove-mentioned especially preferred
or lower, and is reversible by the indicated radiation
actants which are speci?ed, in, said speci?c embodiment
radiation when it is in the undissolved state, such as in
dry crystalline form or as an undissolved liquid dispersion.
With regard to this particular compound, if "a near
saturated solution of it in toluene in the colorless state is
within the temperature range of drum plus 20 degrees
compounds (1) to (5), inclusive, the speci?c process to
centigrade to minus 20 degrees .centigr'ade. The corn
be described hereinafter for preparing the 5’,7’-dichloro—
pound is stable in either the colored state or the uncolored
6'-nitro derivative is followed exactly; that is, the same
process steps ‘as well as the same proportions of re 45 state even in the‘presence of color-change-provokmg
of the process are used; " More speci?cally, compounds
(1) to (5), inclusive, are prepared by condensing com~
mercially-available 2-rnethylene—1,3,3 - trirnethyl-indoline 50
changed to the colored ‘form by irradiation with ultra
with the following substituted salicylaldehydes, respec
violet light, part of the colored compound will precipitate
tively, all of which areeither known or 'which may
out because of a decrease in its solubility. However,
readily be prepared by those skilled in the art:
(1)
Cl
N 02
01
j
'
'
——CHO
changed to the colorless form on continued reversing
radiation.
This 5',7'-dichloro, 6'-nitro derivative compound can
—OH
4,6-dichlor0‘5-nitrosa1icylaldehyde
(2)
upon reversing radiation, the portion remaining dis-solved
will ?rst change back to the colorless state, allowing the
55 remaining precipitated part to dissolve and become
60
NO;
NO
be made by adding an aldehyde group to the commer
ciallyaiavailable 3,5-dicl1lorophenol by a Reimer-Tienrann
reaction to produce 4,6-'dichlorosalicylaldehyde, as
follows:
-CHO
—OH
(In!
65
'
.'
c1101
I
00133
‘3~metl1oxy-5,G-dinitrosalicylaldehyde
.(a)
N0
—CHO
—OH
(‘>11
'
3
0110-
on
01-
~01
Cl
—01
which is carried out speci?cally
follows:
In a ?ve-liter, three-necked standard round-bottom
?ask, ?tted with a Friedrich condenser, a dropping \fun
nel, a motor-driven stirrer, and a thermometer, are placed
280 ‘grams of calcium hydroxide, 320 grams of sodium
75 carbonate, 142 grams (0.875 mole) of 3,5-dichlorophenol,
and 1,500 milliliters of distilled water. With stirring, the
3,100,778
6
The compound may be changed to the all-colored or
the all-colorless state by being irradiated in solution with
added, drop by drop, 209 grams (1.75 moles) of chloro
the selected radiation. The color of the colored form
form at a rate to maintain the temperature between 55
dissolved in various solvents may differ; ‘for instance,
degrees and 60 degrees centigr-ade, over a period of about
three hours. The newly-formed yellow mixture then is Cl the compound dissolved in toluene is blue, but dissolved
in ethanol. is red.
7
maintained at 65 degrees to 70 degrees centigrade for
As contrasted with the 5’,7’ dichloro 6'-nitro com
three hours, cooled to room temperature (22 degrees
mixture is heated to 55 degrees Centigrade, after which is
pound just discussed, the 6’,8' dinitro derivative com
pound has anexpression value of‘5.377+, which is outside
drochloric acid. The foregoing acidi?ed mixture then is
steam-distilled directly from the reaction ?ask until the 10 the acceptable range as de?ned by the expression. This
6’,8’ dinitro compound, while having, in solution, a color
distillate is no longer cloudy. Six liters of the distillate
less state which may be induced by the mentioned visible
are collected and allowed to stand for four hours at room
and infra-red components specially directed on it, spon
temperature. This yields a pale-yellow crystalline pre
taneously reverts to the colored form, at room. tempera
cipitate, which is recovered on a suction ?lter‘ and air
ture, by thermal activity, in the absence of special ra
dried to give 50.1 grams (30%) of 4,6-dichlorosalicylal
centigrade), and acidi?ed to pH 2 with concentrated hy
diaticn.
dehyde.
For derivatives not satisfying the expression by being
The 4,6-dichlorosalicylaldehyde then is nitrated by the
following reaction:
01
below the lower end of the range may be considered the
6'-nitro derivative compound, which has an expression
20 value of 2.64957. This compound is changed to the col
ored form'by ultra-violet radiation at room temperature,
reverts spontaneously to the colorless form in the dark,
(In
—ono HONOZ N02
_ono
----——>
or
-on
Ho“
01-
and, hence, is entirely useless for the purposes named.
Next will be described the compound
_on
which is carried out speci?cally as follows:
‘
A solutionof 10 grams (0.053 mole) of 4,6-dichloro
salicylaldehyde in 25 milliliters of glacial acetic acid is
cooled in a water bath to 18 degrees Centigrade, with stir
ring. Over a period of thirty minutes, 10 milliliters
(0.215 mole) of fuming nitric acid, minimum of 90% 30
nitric acid, is added. The temperature is gradually raised
to 45 degrees centigrade, and then‘ the mixture is poured
into 600 milliliters of ice and water.
The product is re
which has an expression value of 3.2326+ and is within
the expression range but near its lower end point of 3.110.
covered by ?ltration, washed thoroughly with cold water,
and dried. The crude product is recrystallized from ethyl
alcohol to give 2.4 grams (20%) of 4,6-dichloro-5-nitro—
This compound is made by the nitration of S-brornosali
cylaldehyde, a commercially-available compound, and
salicylaldehyde.
condensing it with 2-methylene-1,3,3-trimethylindoline,
This last-recovered material is condensed with the com
mercially-available Z-methylene-1,3,3-trimethylindoline in
ethyl alcohol, according to the following reaction, shown
structurally:
H30
CH3
Cl .
\
NO
OHO 02115013:
=CH2 +
/
--———e
C1——
----OH
before mentioned, by the same process before described.
40 This compound dissolved in ethanol is colorless when the
2'-1’ bond is intact and has a red color when the 2’-l'
bond is broken, by the described radiation, and is ther
mally stable in either condition within the speci?ed tem
perature range.
45 'All of the derivate compounds included within the
terms of the expression may be made by condensing
2—methylene-1,3,3-trimethylindoline with salicylaldehyde
1?CH3
having the selected substituents from Table I, in‘ the de
use
4
5
G
scribed manner.
on;
><
3
well known to those familiar with the art.
In selecting substituents from Table I, care should be
‘taken to include in the same compound only substituents
‘
\
The substituted components of the con
50 densation may be made as noted herein or by procedures
I
I
1 / \lol
by?
on,
NO
—
I
which are sterically compatible in the sense that they will
not interfere with that resonance in the compound neces
sary to produce color when the 2'-1' bond is broken.
or
which is carried out speci?cally as follows:
In a ZSO-milliliter round-bottom ?ask ?tted with a
‘The following list includes a number of compounds.
within the expression and having sterically compatible sub
stituent's, together with their total sigma values ‘and their
Friedrich condenser is placed 100 milliliters of absolute
ethanol, 3.46 ‘grams (0.02 mole) of 2~rnethylene-1,3,3- ‘
expression values, the colored form being red. when dis
solved in ethanol and dark blue when ‘dissolved in toluene:
trimethylindoline, and 4.72 grams (0.02 mole) of 4,6
dichloro-S-nitrosalicylaldehyde. The resulting purple so
lution is re?uxed for two hours and then cooled in an ice
2 @(R1' )
bath to produce a crystalline precipitate. The crystalline
product is recovered by ?ltration, washed in cold ethanol,
and ‘air-dried. The yielded‘ product is 1,3,3-trimethylin
‘II/Sass,
doline-S',7’-dichloro-6’-nitrobenzopyrylospiran, which by
combustion analysis calculated for C19H15N2O3Cl2: C,
58.3%‘; H, 4.1%. Found: C, 58.2%; H, 4.0%.
The newly-synthesized compound may have some mole- ‘
,cules wherein the 2'—1’ bond is broken and some in which
such bond is intact, depending on the solvent liquid in
which the reaction is carried out.
Polar solvents tend to
favor the colored state, in which the 2’-1’ bond is broken,
and non~polar solvents tend to favor the colorless state,
in which the 2L1’ bond is intact.
‘
‘
value
6’-nltro-5',7’-diehl0ro ___________ -_- ______ __
1. 523
5. 19343
_ _ _ _ ._
1. 350
4. 60350
5’ ,6’ ,8’ -trichloro-7’ -11itro_-_
___________ __
1. 347
4. 59327
1. 227
1. 150
1. 049‘
l. 017
4. 18407
3. 92150
3. 57709
3. 46797
6’-nitro-8’-iodo ..... __
6’-nitro-8’-bromo _______________________ __
. 987'
. 987'
3. 36567
3. 36567
5’ -nltrO-6’ ,8’-dichl0ro ______ __
. 971
3. 32134
6’-bromo-8'-nitr0-.
6'-i0do<8’-nitro . _ . _ _
6’-ehlor0-8’-nitro_._
75
Expression
6’-nitro-7’,8’—dichloro _ _ _ . _
6’-nitro-8’-corbomethoxy__
6’-nitro-7’-ehloro-____
5’-6’-dinitro-8’~methox
6'-nitro-8’-?u0r0____.
1
I (1
_ _ _ __
. 9&8
3 23268
. 932:
3. 17812
912:
3. 10992
3,100,778
8
The thermal stability of the novel compounds of this
invention may be quantitatively determined by measuring
pound material to the uncolored form, as described. The
the half-life of solutions of said compounds, such as
temperature and below, and, because the capsules retain
the novel material in liquid solution, the sheet may be
marks so made are substantially stable thermally at room
ethanol solutions thereof, while taking care that such solu
tions are maintained at constant temperature, such as 6 5 erased and remarked many times. In addition, the cap
degrees centigrade, and are protected from exposure to
sules may be broken by pressure to evaporate the toluene
electromagnetic radiation. Methods for determining the
and leave the novel compound material in solid form
to make any marks made permanent even if irradiated with
half-life are well known and commonly involve the estima
tion of the decrease in absorbency of the compound solu
tion by means of a spectrophotometer. '
The value of the half-life so obtained is a quantitative
measure of the time required for one-half of the molecules
in the visibly-colored form to revert to the visibly-colorless
form, the solution being in the dark and maintained at a
?xed temperature.
'
The surprisingly and unexpectedly long half-lives of
representative compounds selected from the high, medium,
erasing radiation.
10
.
The novel material claimed has many other uses, as in
indicator and light-?ltering applications wherein the color
change brought about by incident light is to be thermally
stable.
What is claimed is:
15
1. A compound of the formula
H30
CH3
and low range of exprcssionvalues listed above appear
in the following table:
'
20
Derivative oi 1,3,3
trlmet hyl-spiro-
(2’H-1’-benzopy-
ran-2,2’~indoline)
6'-N Oz- 5’) 6’-N Oz- 6’-N Oz-
5’,7’-Ol
8 ~OOH3
8’-F
Days
Days
Min.
6’—N O z-
5'-N Oz
Min.
Min.
8’-Br
6’,8’-Cl
25
Hall-life _________ __
20. 5
34. 2
l, 800
3, 100
wherein Ri is at least two members independently selected
from the class consisting of —NO2, —OCH3, —-Cl, --Br,
——I, and —'F; said independently selected members con
2, 080
sisting of:
.
I
(a) at least one but no more than two -—NO2 groups
By way of comparison, the half-life of the 6'-NO2 deriv
and,
-
a
(b) yat least one member from said class other than
ative, heretofore mentioned, is only 268 minutes. Thus,
the —-NO2 group,
it is apparent that some of the compounds described and
said members being so selected that the compound, when
claimed herein are nearly 200 times more stable to thermal
dissolved in ethanol, satis?es the expression:
ly-induced color change than the 6'-NO2 derivative.
As an indication of the utility of these compounds, a 35
liquid solution of any one of them, or a mixture of any
3109925341
of them in liquid solution, may be dissolved in toluene,
emulsi?ed in a gelable colloid solution as microscopic
’ droplets, and each droplet surrounded by an enclosing wall
s'sqss'
0(R’i, q)55.19343
wherein Ri represents the selected class members, q stands
of the colloid gelled to a solid, to form a solid-walled , 40 for the ring positions to which such members are attached,
microscopic capsule containing in liquid form a drop
and
let of the solution. This encapsulation may be accom
plished according to the coacervation process described in
Z a Rt. q)
United States Letters Patent No. 2,800,457, which issued
on the application‘ of Barrett K. Green and Lowell
Schleic‘he-r on July 23, 1957. As an example of form
ing the tiny capsules, a sol is made of 20 grams of gum
arabic dissolved in 160 grams of water. Into this is emul
si?ed 80 grams of the toluene solution containing the se
lected light-sensitive compound. A second sol of 20
F5458’
45
.
' represents the sum of the substituent constant sigma values
of said selected members when attached at independently .
selected v5', 6', 7', and 8' ring positions, and wherein said
values are as follows:
grams of pork-skin gelatin, having its iso-electric point at
pH 8, and 160 grams of water is prepared, and this sec
ond sol is mixed with the emulsion. A volume of Water
then is added slowly to the mixture drop by drop, or by
+0. 80
spray, with constant stirring until coacervation starts and
is continued until the particle size of the toluene droplets
on which the coacervate material is deposited is as large
as desired, the less Water used the smaller the particle
size. All of-the foregoing steps are carried out with, the
ingredients at 50 degrees Centigrade.
The resulting 60
coacervate mixture is poured into water at 0 degrees cen
trigrade, enough water being used to bring the total weight
of ingredients to 3960 grams. The mixture is agitated
and thereafter is allowed to stand for an hour at not over
25 "degrees centigrade. The formation of the capsules is 65
now completed, and they may be used in suspension as a
coating for surfaces or for other use as a ?uid, or they
may be dried and comminuted.
The capsules so made may be coated on a sheet of paper
and dried. This sheet may be used to record data by ap
plying ultra-violet light to selected, spots thereon to produce
a blue mark against the background color of the paper.
Such marks may be sensed by photo-electric pick-up
means. When the user is through with the data, the marks
may be erased with light which changes the novel com
+0. 062
+0. 777
-—0. 30
—0. 0465
-—0. 764
+0. 20
+0. 21
0. 21
+0. 24
+0. 373
+0. 391
+0. 352
+0. 337
+0. 112
+0. 148
+0. 132
—-0. 0714
2. The compound l,3,3~trimethylindoline-5’,7'-dichloro
6'-nitrobenzopyrylospiran.
'
_
3. The compound l,3,3-trimethylindoline-8'-methoxy
5',6idinitrobenzopyrylospiran.
4. The compound 1,3,3-trimethylindolino-8’-?uoro-6'
nitrobenzopyrylospiran.
5. The compound 1,3,3-trimethylindolino-8'-bromo-6'
nitrobenzopyrylospiran.
'
6. The compound 1,3,3-trimethylindolino-6',8'-chloro
5’-nitrobenzopyrylospiran,
.
‘
‘
References Cited in the ?le‘ of this patent
UNITED STATES PATENTS
2,953,454
'
Berman ____________
__Q_ Sept. 20, 1960
(Other references on following page)
3,100,778
9
,
OTHER REFERENCES
' '
a1.: H
t'
c 'l
'
A
10
Hirshberg et a1.: J.__Chem. Soc. (London), pages 3129
>
pagézlzll’éff?i (1940)e_1ve 103' hnmca cta’ volume
23,
37 (1954)
Hirshberg: J. Amer. Chem. 800., volume 78, pages
Koelsch et a1.: J. Amer. Chem. 800., volume 74, pages
2304'12 (1956)'
5238_9. (1952)_
5
Berman et al.: J. Amer. Chem. Soc., volume 81, pages
5605-5608 (1959).
Claude et ‘a1.: Compt._Rendus, volume 236, pages 697
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